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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2065.
Published online 2010 July 21. doi:  10.1107/S1600536810028047
PMCID: PMC3007541

4-Ethyl­anilinium 4-methyl­benzene­sulfonate

Abstract

In the crystal structure of the title molecular salt, C8H12N+·C7H7O3S, the 4-ethyl­anilinium cations and 4-methyl­benzene­sulfonate anions are linked into chains parallel to the b axis by inter­molecular N—H(...)O hydrogen bonds.

Related literature

For background literature concerning mol­ecular–ionic compounds, see: Czupiński et al. (2002 [triangle]); Katrusiak & Szafrański (2006 [triangle]). For related structures. see: Chen (2009 [triangle]); Wang (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2065-scheme1.jpg

Experimental

Crystal data

  • C8H12N+·C7H7O3S
  • M r = 293.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2065-efi1.jpg
  • a = 25.016 (3) Å
  • b = 5.6376 (11) Å
  • c = 21.6387 (13) Å
  • β = 95.227 (10)°
  • V = 3039.0 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 291 K
  • 0.36 × 0.28 × 0.24 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.930, T max = 0.950
  • 14572 measured reflections
  • 3490 independent reflections
  • 2614 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.178
  • S = 1.06
  • 3490 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028047/rz2476sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028047/rz2476Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the China Postdoctoral Science Foundation funded project (20090451147), the Jiangsu Planned Projects for Postdoctoral Research Funds (0802003B) and the SEU Major Postdoctoral Research Funds (3212000901) for financial support.

supplementary crystallographic information

Comment

Recently much attention has been devoted to simple molecular–ionic crystals containing organic cations and anions due to the tunability of their special structural features and their interesting physical properties (Czupiński et al., 2002; Katrusiak & Szafrański, 2006). For similar structures, see: Chen, 2009; Wang, 2010. In our laboratory, the title compound has been synthesized and its crystal structure is herein reported.

The asymmetric unit of the title compound consists of a 4-ethylanilinium cation and a 4-methylbenzenesulfonate anion (Fig 1), in which proton transfer from the acid to the basic component has occurred (Fig. 1). In the crystal packing (Fig. 2), cations and anions are linked into one-dimensional chains parallel to b-axis by intermolecular N—H···O hydrogen bonds (Table 1).

Experimental

4-Methylbenzenesulfonic acid hydrate (1.90 g; 10 mmol) was firstly dissolved in 50 ml ethanol, to which 4-ethybenzenamine (1.21 g; 10 mmol) was added under stirring at the ambient temperature to afford a clear solution without any participation. Single crystals suitable for X-ray structure analysis were obtained by slow evaporation of the above solution after 5 days in air (m. p. 192 °C).

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent (ε = C/(T–T0)), suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature range between 93 K and 455 K.

Refinement

H atoms were placed in calculated positions (N—H = 0.89 Å; C—H = 0.93 Å for Csp2 atoms and C—H = 0.96 Å and 0.97 Å for Csp3 atoms), assigned fixed Uiso values [Uiso = 1.2Ueq(Csp2, N) and 1.5Ueq(Csp3)] and allowed to ride.

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme with 30% probability displacement ellipsoids.
Fig. 2.
Crystal packing of the title compound viewed along the a axis. Hydrogen atoms not involved in hydrogen bonds (dashed lines) are omitted for clarity.

Crystal data

C8H12N+·C7H7O3SF(000) = 1248
Mr = 293.38Dx = 1.283 Mg m3
Monoclinic, C2/cMelting point: 465 K
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 25.016 (3) ÅCell parameters from 12307 reflections
b = 5.6376 (11) Åθ = 3.1–27.6°
c = 21.6387 (13) ŵ = 0.22 mm1
β = 95.227 (10)°T = 291 K
V = 3039.0 (7) Å3Block, colourless
Z = 80.36 × 0.28 × 0.24 mm

Data collection

Rigaku Mercury2 diffractometer3490 independent reflections
Radiation source: fine-focus sealed tube2614 reflections with I > 2σ(I)
graphiteRint = 0.048
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.3°
CCD_Profile_fitting scansh = −32→32
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −7→7
Tmin = 0.930, Tmax = 0.950l = −27→28
14572 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.178H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0988P)2 + 1.990P] where P = (Fo2 + 2Fc2)/3
3490 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.44 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.18002 (12)0.6568 (8)0.1475 (2)0.0771 (11)
H1A0.16360.78690.12430.116*
H1B0.16340.63860.18550.116*
H1C0.17540.51380.12350.116*
C20.23944 (10)0.7059 (5)0.16208 (13)0.0448 (7)
C30.26270 (11)0.9123 (6)0.14269 (15)0.0549 (8)
H3A0.24141.02310.12010.066*
C40.31647 (11)0.9576 (5)0.15593 (14)0.0471 (7)
H4A0.33111.09850.14280.056*
C50.34871 (9)0.7941 (4)0.18873 (10)0.0304 (5)
C60.32643 (10)0.5882 (5)0.20886 (13)0.0416 (6)
H6A0.34780.47690.23120.050*
C70.27173 (11)0.5477 (5)0.19556 (13)0.0473 (7)
H7A0.25680.40940.20980.057*
C80.32058 (15)0.5450 (11)0.52795 (18)0.1058 (18)
H8A0.30260.58950.56350.159*
H8B0.31300.38190.51800.159*
H8C0.30820.64320.49330.159*
C90.37861 (13)0.5763 (7)0.54173 (14)0.0620 (9)
H9A0.39080.47850.57710.074*
H9B0.38590.74040.55300.074*
C100.41024 (10)0.5113 (5)0.48754 (12)0.0414 (6)
C110.41036 (12)0.6573 (5)0.43615 (13)0.0473 (7)
H11A0.39190.80060.43580.057*
C120.43700 (11)0.5966 (5)0.38534 (12)0.0420 (6)
H12A0.43650.69690.35120.050*
C130.46425 (9)0.3857 (4)0.38629 (11)0.0317 (5)
C140.46589 (10)0.2380 (5)0.43700 (12)0.0417 (6)
H14A0.48510.09670.43750.050*
C150.43868 (11)0.3020 (5)0.48717 (13)0.0467 (7)
H15A0.43960.20190.52140.056*
N10.49149 (8)0.3138 (4)0.33224 (9)0.0373 (5)
H1D0.48740.42610.30330.056*
H1E0.47740.17860.31710.056*
H1F0.52630.29310.34350.056*
O10.44138 (7)0.6248 (4)0.22484 (10)0.0543 (6)
O20.42345 (8)1.0277 (4)0.25272 (9)0.0534 (5)
O30.43719 (8)0.9314 (4)0.14712 (9)0.0575 (6)
S10.41818 (2)0.84917 (11)0.20463 (3)0.0335 (2)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0355 (16)0.105 (3)0.089 (3)−0.0119 (18)−0.0011 (16)−0.011 (2)
C20.0313 (13)0.0591 (18)0.0439 (14)−0.0054 (12)0.0019 (11)−0.0108 (13)
C30.0425 (15)0.0547 (18)0.0650 (19)0.0104 (13)−0.0090 (14)0.0114 (16)
C40.0420 (14)0.0369 (14)0.0616 (18)−0.0030 (12)0.0007 (12)0.0127 (13)
C50.0289 (11)0.0313 (12)0.0311 (11)−0.0021 (9)0.0031 (9)−0.0010 (9)
C60.0387 (13)0.0366 (14)0.0486 (15)−0.0047 (11)−0.0004 (11)0.0118 (12)
C70.0450 (15)0.0435 (16)0.0543 (16)−0.0164 (13)0.0093 (12)0.0019 (13)
C80.068 (2)0.188 (5)0.067 (2)−0.008 (3)0.032 (2)−0.023 (3)
C90.069 (2)0.076 (2)0.0434 (16)0.0024 (18)0.0176 (15)−0.0095 (17)
C100.0435 (14)0.0475 (15)0.0338 (13)−0.0005 (12)0.0067 (11)−0.0056 (12)
C110.0578 (17)0.0398 (15)0.0454 (15)0.0134 (13)0.0117 (13)−0.0001 (12)
C120.0542 (16)0.0352 (14)0.0373 (14)0.0034 (12)0.0084 (11)0.0060 (11)
C130.0303 (11)0.0342 (13)0.0308 (12)−0.0043 (10)0.0037 (9)−0.0019 (10)
C140.0441 (14)0.0363 (14)0.0449 (15)0.0076 (12)0.0045 (12)0.0071 (12)
C150.0531 (16)0.0511 (17)0.0360 (14)0.0065 (13)0.0055 (12)0.0122 (12)
N10.0373 (11)0.0397 (12)0.0355 (11)−0.0024 (9)0.0067 (8)−0.0065 (9)
O10.0368 (10)0.0510 (12)0.0746 (15)0.0090 (9)0.0017 (9)0.0067 (11)
O20.0467 (11)0.0567 (13)0.0561 (12)−0.0120 (9)0.0005 (9)−0.0235 (10)
O30.0493 (12)0.0805 (16)0.0439 (11)−0.0235 (11)0.0106 (9)0.0028 (11)
S10.0288 (3)0.0368 (4)0.0350 (3)−0.0045 (2)0.0031 (2)−0.0028 (3)

Geometric parameters (Å, °)

C1—C21.517 (4)C9—H9A0.9700
C1—H1A0.9600C9—H9B0.9700
C1—H1B0.9600C10—C151.378 (4)
C1—H1C0.9600C10—C111.384 (4)
C2—C71.366 (4)C11—C121.379 (4)
C2—C31.383 (4)C11—H11A0.9300
C3—C41.374 (4)C12—C131.370 (3)
C3—H3A0.9300C12—H12A0.9300
C4—C51.378 (3)C13—C141.375 (3)
C4—H4A0.9300C13—N11.463 (3)
C5—C61.375 (3)C14—C151.381 (4)
C5—S11.768 (2)C14—H14A0.9300
C6—C71.391 (4)C15—H15A0.9300
C6—H6A0.9300N1—H1D0.8900
C7—H7A0.9300N1—H1E0.8900
C8—C91.466 (5)N1—H1F0.8900
C8—H8A0.9600O1—S11.443 (2)
C8—H8B0.9600O2—S11.4451 (19)
C8—H8C0.9600O3—S11.448 (2)
C9—C101.518 (4)
C2—C1—H1A109.5C8—C9—H9B109.0
C2—C1—H1B109.5C10—C9—H9B109.0
H1A—C1—H1B109.5H9A—C9—H9B107.8
C2—C1—H1C109.5C15—C10—C11117.7 (2)
H1A—C1—H1C109.5C15—C10—C9121.1 (3)
H1B—C1—H1C109.5C11—C10—C9121.1 (3)
C7—C2—C3117.7 (2)C12—C11—C10122.0 (2)
C7—C2—C1120.8 (3)C12—C11—H11A119.0
C3—C2—C1121.5 (3)C10—C11—H11A119.0
C4—C3—C2121.6 (3)C13—C12—C11118.6 (2)
C4—C3—H3A119.2C13—C12—H12A120.7
C2—C3—H3A119.2C11—C12—H12A120.7
C3—C4—C5119.9 (3)C12—C13—C14121.1 (2)
C3—C4—H4A120.0C12—C13—N1119.7 (2)
C5—C4—H4A120.0C14—C13—N1119.2 (2)
C6—C5—C4119.5 (2)C13—C14—C15119.2 (2)
C6—C5—S1120.41 (19)C13—C14—H14A120.4
C4—C5—S1120.08 (19)C15—C14—H14A120.4
C5—C6—C7119.5 (2)C10—C15—C14121.3 (2)
C5—C6—H6A120.2C10—C15—H15A119.3
C7—C6—H6A120.2C14—C15—H15A119.3
C2—C7—C6121.7 (3)C13—N1—H1D109.5
C2—C7—H7A119.2C13—N1—H1E109.5
C6—C7—H7A119.2H1D—N1—H1E109.5
C9—C8—H8A109.5C13—N1—H1F109.5
C9—C8—H8B109.5H1D—N1—H1F109.5
H8A—C8—H8B109.5H1E—N1—H1F109.5
C9—C8—H8C109.5O1—S1—O2112.62 (13)
H8A—C8—H8C109.5O1—S1—O3112.74 (14)
H8B—C8—H8C109.5O2—S1—O3112.34 (13)
C8—C9—C10113.0 (3)O1—S1—C5105.43 (11)
C8—C9—H9A109.0O2—S1—C5106.63 (11)
C10—C9—H9A109.0O3—S1—C5106.43 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1D···O1i0.892.242.792 (3)120
N1—H1D···O10.892.263.085 (3)154
N1—H1E···O2ii0.892.042.815 (3)146
N1—H1F···O3iii0.892.242.808 (3)122

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x, y−1, z; (iii) −x+1, y−1, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2476).

References

  • Chen, L.-Z. (2009). Acta Cryst. E65, o2626. [PMC free article] [PubMed]
  • Czupiński, O., Bator, G., Ciunik, Z., Jakubas, R., Medycki, W. & Swiergiel, J. (2002). J. Phys. Condens. Matter, 14, 8497–8512.
  • Katrusiak, A. & Szafrański, M. (2006). J. Am. Chem. Soc.128, 15775–15785. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, B. (2010). Acta Cryst. E66, o1473. [PMC free article] [PubMed]

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